Method of recovering lithium from minerals



umene, for example,

Patented Oct. 12,- 1943.

Y um'rao STATES. PATENT OFFICE Axel Rudolf Lindblad and Sven Johan Stockholm, and Karl Arne Sivander,

assignors to Bolidens Gruvak- Sweden,

hamn, Sweden, tiebolag,

Stockholm,

Walldn,

stock company of Sweden No Drawing. Application June 20, 1939, Serial No.

Claims.

The present invention refers to a method of recovering lithium from lithimncontaining minerals, such as amblygonite, lepidolite, pet-'- alite, spodumene and so forth, by lixiviation with an aqueous solution of metal salts.

A number of methods of extracting lithium from the minerals thereof are previously known.

280,152. In Sweden June 22, 1938 Those methods which have reached some im- I portance are based on acid methods of decomposition and on ion exchanging reactions between alkaline compounds or compounds of the alkaline earths and the mineral at temperatures above 800 degrees centigrade.' The acid methods of decomposition sufier from the disadvantage that the whole mineral skeleton 'is destroyed and dissolved. Great dimculties are then met within separating out non-desirable dissolved compounds. Only where the working of high-percentage minerals, such as amblygonite, is brought into consideration would the .method be of any practical importance. The

7 methods of recovering lithium by means of an exchanging reaction involve a great advance as against the methods just mentioned. This group of methods comprises the known methods of technical working silicate minerals. Hereby, a commercial exploitation of rather lowpercentage lithium ores has been rendered possible. The working costs are still considerable, however, by reason, inter alia, of great heating costs, expensive reaction agents (potassium sulphate), expensive grinding of the-mineral, and expensive furnace apparatus. I

We have worked out a third type of extractmg method which will considerably simplify the working of the minerals and render such worktinguis'h'ed by the feature that the lithium content of the minerals is lixiviated by means of a water solution of neutral metal salts.

' subsidiary reactions are prior to the lixiviation process. At the heating,

the minerals will break through heat tensions. In some cases, as heating of spodumene, recrystallisations will also set in within the material, whereby this breaking is increased still more. This breaking of the minerals augments the mineral surface and makes it easier to crush the mineralgrains. I

The extracting reaction progresses comparatively slowly when the lixiviation is undertaken at ordinary temperature, by reason of which the lixiviation is generally performed at a temperature of 100 to 300 degrees centigrade' and at a pressure above atmospheric. Recovery of lithium according to the method above described may be carried out with'a good yield. Subsidiary reactions may set in, however, during the progress of the main reaction, which responsible for the fact that the reaction of the lixiviation is rendered acid. It will then be found that the rapidity oi the dissolving-out process for the lithium of the mineral may be reduced abnormally rapidly. Consequently, after lixiviation for some hours has proceded, the rapidity of reaction may be reduced to nearly zero. Therefore, if coarseit may be posonly of the total contents of alkaline metals of the minhaving an exceedingly large reaction surface ing cheaper. This novel type of method is dis- Metal salts which have proved particularly suitable for this dissolving-out operation, are salts of sodium and potassium and the metals of the alkaline earths. In the working of spodwith a'sodium sulphate solution, lithium and other alkalis more or less enter into solution as sulphates, while sodium ions enter into the mineral from the solution and are bound in place of the dissolved-out ions. In the llxiviation of the minerals in their natural state, the ion exchange slowly. It will be found to be advantageous, therefore, to heat the minerals to a high temper-attire, such as 700 to 1200 degrees centlgrade,

takes place rather per unitoi weight. To produce such a material, the mineral is first preferably roasted and then ground very finely. Both of these procedures call for expensive apparatus and are expensive 5 to carry into efiect. Moreover, it will be necessary to make the apparatus wherein the lixiviation is carried out from expensive acid proof material.

We have also found that these difllculties may be obviated by an admixture to the lixiviating solution of small quantities of some substance producing an alkaline reaction, such as sodium hydroxide, sodium carbonate, lime and so forth.

The apparatus may be made from ordinary iron and the rapidity of reaction can be maintained.

at a high level for a long time. Furthermore, the advantage is obtained that iron and aluminium that might be dissolved out from the mineral is precipitated from the solution in the process of lixiviation and may be filtered ofi together with the rest of' the liquor.

While the inventors do not wish to be bound 2 4 by any particular theory of operation, lieved that the maintenance of the rapidity of re- Such lixiviating sowith petalite the best yields are obtained at an admixture of lime of about 60 g. per kilogram of Detalite.

The most suitable salts for the lixiviating solution are the alkali metal salts.

ter and labour.

, We have found it to be advantageous in lixlviating lithium minerals with this way. In the lixiviation of spodumene with a sodium-nitrate-solution, it will thus be pos- Hereinabove, the use of alkali metal salts pri- 'y has been considered as other neutral metal salts as well.

state of equilibrium between the lithium percentreat excess of the ions that are to mineral.

drive out the The excess may those ions by means of which the displacement is efl'ect'ed.

To every temperature corresponds a definite strong base which, if sodium sulphate be used as a reaction agent, is constituted by sodium hydroxide. The alkali metal sulphate formed at the same time crystallizes out together with enterlng alkali metal sulphate by cooling to a temperature in the proximity of degree centigrade. After the sulphate has been filtered oil, the mother liquor obtained is evaporated, pure lithium hydroxide being thus caused to crystallize.

Theadvantage of this method of producing lithium hydroxide resides, above all, in the fact that the costs of evaporation and labour become small. a

What we claim is: a

1. A method of recovering lithium from a lithium-containing mineral which comprises lixiviating the mineral with an aqueous solution 0! a neutral metal salt containing a substance producing an alkaline reaction, the amount of alkaline reacting substance added to said aqueous solution being not more than about 6% by weight of the amount oi lithium-containing mineral be.- ing treated, and being sufilcient' to prevent the precipitation of silicic acid as a gel on the mineral surfaces but insufllcient to materially increase the amount of siliceous material dissolved out of the mineral.

2. A method of recovering lithium from a lithtral metal salt, further characterized in that'the mineral is lixiviated with a solution 0:! an alkali metal sulphate, thereafter alkali metal hydroxide is added to the solution of lithium sulphate so obtained, the sulphate salts are crystallized out by cooling, and lithium hydroxide is recovered by evaporation.

5. In a method for recovering lithium-from a naturally-occurring lithium-containing mineral,

the steps comprising lixiviating the mineral with awater solution of a neutral metal salt containing in addition at least one substance .producing an alkaline reaction selected from the group con- Y sisting of hydroxides of alkali metals and hydroxides of alkaline earth metals in an amount sufllcient toprevent precipitation 01! silicic acid as a gel on the mineral surfaces but insumcient to materially increase the amount of siliceous material dissolved out of themineralfthereby obtaining a lixivium containing lithium in the form oi a relatively water-soluble compound ium-containing mineral which comprises lixiviating the mineral with an aqueous solution oi a neutral metal salt containing a substance producing an alkaline reaction, the amount of alkaline reacting substance added being sufllcientto prevent the precipitation 01 silicic acid as a gel on the mineral surfaces but insufllcient to materially increase the amount 01 siliceous material dissolved out o! the mineral.

3. A method of recovering lithium from a lithium-containing mineral which comprises lixiviating the mineral with a'water solution of a neutral metal salt, iurther characterized in that at least one substance producing an alkaline reaction is added to the'metal salt solution in suit!- cient quantity such that, alter the lixiviation hasbeen completed, the solution will still have an alkaline reaction.

4. A method oi recovering lithium from a lithium-containing mineral which comprises lixivilting the mineral with a water solution 1 a neuthereof; and recovering lithium compound from said lixivium.

6. A method for recovering lithiumirom a naturally-occurring lithium-containing mineral comprising lixiviating'the mineral with a water solution of a neutral metal salt containing lime in an amount sufficient to prevent precipitation oi silicic acid as a gel on the mineral suriaces but insufllclent tomaterially increase the amount of siliceous material dissolved out oi the mineral, thereby obtaining-a lixivium containing lithium in the form of a relatively water-soluble compound thereof; and recoveringlithium compound irom said lixivium.

7. A method as in claim 2', in which the neutral metal salt is an alkali metal salt.-

8. A method as. in claim 2, in which the neutral metal alt is sodium sulphate.

'9. A method as in claim 2, in which the neutral metal salt is sodium chloride. l

10. A method as in claim 2, in which the step or iixiviation is performed at a temperature between and 300' C.,-and at a corresponding,

superatmospheric pressure.

AXEL RUDOLF LINDBLAD.

, fsvau 'Jonmwammtm,

mmamm srvasnna. 

